Abstract
A general systematic polyad breaking approach based on Van Vleck perturbation theory is proposed for anharmonic systems where interacting Morse and/or Pöschl–Teller (PT) potentials are considered to describe molecular vibrational excitations in the framework of local mode models. Our approach is based on the algebraic representation of the Hamiltonian via the realization of the coordinates and momenta as an expansion in terms of creation and annihilation operators of Morse and/or PT functions. This algebraic representation permits to establish a perturbation expansion of the Hamiltonian suitable to apply Van Vleck perturbation theory. As an example to assess our approach a Hamiltonian of two interacting Morse oscillators with a coupling potential bilinear in the Morse coordinates is analysed in detail. Successive corrections to energies as well as to wavefunctions are presented.
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